US9242904B2 - Aqueous preparations of polymer-modified setting accelerators, and use thereof in the construction industry - Google Patents
Aqueous preparations of polymer-modified setting accelerators, and use thereof in the construction industry Download PDFInfo
- Publication number
- US9242904B2 US9242904B2 US12/599,982 US59998208A US9242904B2 US 9242904 B2 US9242904 B2 US 9242904B2 US 59998208 A US59998208 A US 59998208A US 9242904 B2 US9242904 B2 US 9242904B2
- Authority
- US
- United States
- Prior art keywords
- vinyl
- acrylate
- aqueous
- polymers
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
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- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 238000010276 construction Methods 0.000 title description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 125000002091 cationic group Chemical group 0.000 claims description 25
- 239000000084 colloidal system Substances 0.000 claims description 22
- 230000001681 protective effect Effects 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 17
- -1 carboxylic acid radical Chemical class 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 229920001567 vinyl ester resin Polymers 0.000 claims description 12
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 5
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 claims description 5
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 5
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 5
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- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- IQYMRQZTDOLQHC-ZQTLJVIJSA-N [(1R,4S)-2-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@H]2C(OC(=O)C=C)C[C@@H]1C2 IQYMRQZTDOLQHC-ZQTLJVIJSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 claims description 3
- IGBZOHMCHDADGY-UHFFFAOYSA-N ethenyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC=C IGBZOHMCHDADGY-UHFFFAOYSA-N 0.000 claims description 3
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 claims description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 3
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- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
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- 239000005977 Ethylene Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920005601 base polymer Polymers 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 5
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- NEYTXADIGVEHQD-UHFFFAOYSA-N 2-hydroxy-2-(prop-2-enoylamino)acetic acid Chemical compound OC(=O)C(O)NC(=O)C=C NEYTXADIGVEHQD-UHFFFAOYSA-N 0.000 description 2
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- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000009418 renovation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/04—Alkali metal or ammonium silicate cements ; Alkyl silicate cements; Silica sol cements; Soluble silicate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
- C04B14/303—Alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/10—Acids or salts thereof containing carbon in the anion
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/404—Surface-active agents, dispersants cationic
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
Definitions
- the invention relates to aqueous preparations of polymer-modified setting accelerators, a process for producing them and also aqueous concrete compositions containing aqueous preparations of the polymer-modified setting accelerators, a process for producing them and their use, for example in civil engineering, mining or tunnel construction.
- polymers enables the processability of concrete compositions or the property profile of concrete to be improved, for example its adhesion to various substrates, gas permeability, E modulus, or hydrophobicization of the concrete can be achieved.
- Setting accelerators such as aluminum sulfate considerably accelerate the curing of aqueous concrete compositions and thereby produce better resistance to sagging of the aqueous concrete compositions on their substrate. This simplifies the processing of aqueous concrete compositions and makes vertical or overhead processing possible.
- stiffening times of from a number of minutes to a few seconds can be set by appropriate use of setting accelerators.
- aqueous concrete compositions having different contents of setting accelerators and polymers are frequently required in different construction sections of the same construction site.
- the required adaptation of the composition of the aqueous concrete compositions has, however, hitherto not been possible in a practicable and economical way.
- Previously known compositions containing setting accelerators and polymers are storage-stable only in dry form.
- the entire dry concrete mix would have to be mixed on addition of polymers or setting accelerators, which would be associated with a large outlay in terms of time, apparatus and logistics. It would be more efficient to mix setting accelerators and polymers into the water with which the dry concrete mixes are made up in the spray nozzle.
- the dry spray concrete process is thus not very flexible in respect of the production of aqueous concrete compositions containing variable amounts of setting accelerators and polymers. Furthermore, a large amount of dust is produced in the handling of dry concrete mixes, and this has an adverse effect on the health of the workers on the construction site and makes complicated safety precautions necessary.
- wet concrete mixes comprise cement, fillers such as sand or gravel and, if appropriate, polymers and further additives and have already been made up with water.
- setting accelerators are added to the wet concrete mixes in the spray nozzle, i.e. immediately before application to the respective substrate. It is advantageous that the water content, the consistency and thus the quality of the wet spray concrete can be set precisely when using the wet spray concrete process.
- the wet spray concrete process is particularly suitable when relatively large amounts of concrete compositions are employed, as is the case, for example, in tunnel construction.
- the wet spray concrete process also has the disadvantage that the amount of polymers in the wet concrete mixes cannot be varied on the construction site without a further, complicated mixing step. This is because on addition of polymers to a wet concrete mix, the entire wet concrete mix would have to be mixed, which in view of the large quantities of aqueous concrete compositions to be processed would be associated with a considerable outlay in terms of time and apparatus and additionally represent a considerable change to the established logistics on a construction site.
- aqueous compositions containing setting accelerators and cationically stabilized polymers are stable and do not coagulate or precipitate.
- the invention provides aqueous preparations of polymer-modified setting accelerators, characterized in that one or more setting accelerators and one or more cationically stabilized polymers are present.
- DADMAC diallyldimethylammonium chloride
- DADEAC diallyldiethylammonium chloride
- MTAC (3-methacryloxy)propyltrimethylammonium chloride
- METAC (3-methacryloxy)ethyltrimethylammonium chloride
- MAEMA 2-dimethylaminoethyl methacrylate and 3-dimethylaminopropylmethacrylamide
- DMAPMA species protinated at pH ⁇ 5) diallyldimethylammonium chloride
- DADEAC diallyldiethylammonium chloride
- MTAC (3-methacryloxy)propyltrimethylammonium chloride
- METAC (3-methacrylamido)propyltrimethylammonium chloride
- DMAEMA 2-dimethylaminoethyl methacrylate and 3-dimethylaminopropylmethacrylamide
- the cationic protective colloids contain from 20 to 100% by weight, preferably from 50 to 100% by weight, particularly preferably 100% by weight, of cationic monomer units, based on the total weight of the cationic protective colloid.
- Suitable nonionic, copolymerizable monomers are vinyl esters having from 1 to 15 carbon atoms in the carboxylic acid radical, e.g.
- cationic protective colloids having a K value (determined by a method based on DIN 53726, 1% by weight in water, 25° C., Ubbelohde viscometer) of from 10 to 250, particularly preferably from 25 to 130.
- the modification to DIN 53726, the standard for determination of the viscosity of PVC in an Ubbelohde viscometer, is the use of water instead of cyclohexanone as solvent.
- the Höppler viscosity of the cationic protective colloids is from 1 to 50 mPas, preferably from 1 to 25 mPas, most preferably from 1 to 15 mPas (in each case determined by the Höppler method at 20° C. in accordance with DIN 53015).
- cationic protective colloids is known, for example, from DE-A 102006007282 and can be carried out, for example, by free-radical polymerization in aqueous solution, in solvent mixtures or in the presence of salts, for example also in a precipitation polymerization, for example by polymer-analogs reaction in solution or solvent mixtures, for example in suspension or, for example, by inverse emulsion polymerization.
- Monomers suitable for preparing the base polymer are vinyl esters of unbranched or branched alkylcarboxylic acids having from 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having from 1 to 15 carbon atoms, vinylaromatics, olefins, dienes or vinyl halides.
- Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate. Particular preference is given to methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
- olefins and dienes are ethylene, propylene and 1,3-butadiene.
- Suitable vinylaromatics are styrene and vinyltoluene.
- a suitable vinyl halide is vinyl chloride.
- diethyl and diisopropyl esters and also maleic anhydride, ethylenically unsaturated sulfonic acids or salts thereof, preferably vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid.
- Examples of homopolymers and copolymers suitable as base polymer are vinyl acetate homopolymers, copolymers of vinyl acetate with ethylene, copolymers of vinyl acetate with ethylene and one or more further vinyl esters, copolymers of vinyl acetate with ethylene and acrylic esters, copolymers of vinyl acetate with ethylene and vinyl chloride, styrene-acrylic ester copolymers, styene-1,3-butadiene copolymers.
- VeoVa9®, VeoVa10®, VeoVa11® copolymers of vinyl acetate, from 1 to 40% by weight of ethylene and preferably from 1 to 60% by weight of acrylic esters of unbranched or branched alcohols having from 1 to 15 carbon atoms, in particular n-butyl acrylate or 2-ethylhexyl acrylate; and copolymers comprising from 30 to 75% by weight of vinyl acetate, from 1 to 30% by weight of vinyl laurate or vinyl esters of an alpha-branched carboxylic acid having from 9 to 13 carbon atoms and from 1 to 30% by weight of acrylic esters of unbranched or branched alcohols having from 1 to 15 carbon atoms, in particular n-butyl acrylate or 2-ethylhexyl acrylate, which additionally contain from 1 to 40% by weight of ethylene; copolymers comprising vinyl acetate, from 1 to 40% by weight of ethylene and from 1 to 60% by weight of vinyl chloride; where
- (meth)acrylic ester polymers such as copolymers of n-butyl acrylate or 2-ethylhexyl acrylate or copolymers of methyl methacrylate with nbutyl acrylate and/or 2-ethylhexyl acrylate and, if appropriate, ethylene; styrene-(meth)acrylic ester copolymers comprising one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate-(meth)acrylic ester copolymers comprising one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and, if appropriate, ethylene; styrene-(meth
- the choice of monomers or the choice of the proportions by weight of the comonomers is made in such a way that, in general, a glass transition temperature Tg of from ⁇ 50° C. to +50° C., preferably from ⁇ 30° C. to +10° C., results.
- the glass transition temperature Tg of the polymers can be determined in a known way by means of differential scanning calorimetry (DSC).
- Tgn glass transition temperature in kelvin of the homopolymer of the monomer n.
- Tg values for homopolymers are given in the Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
- the base polymers are prepared in an aqueous medium, preferably by the emulsion polymerization process as described, for example, in DE-A 102006007282.
- the base polymers are obtained in the form of aqueous dispersions and can be converted into corresponding powders which are redispersible in water by customary drying processes.
- the preparation of cationically stabilized polymers which are redispersible in water is carried out, for example, by the method known from DE-A 102006007282 by drying aqueous dispersions of the base polymer, with the cationic protective colloids being able to be added before, during or after drying.
- the cationic protective colloids can also be used in combination with nonionic protective colloids or in combination with nonionic emulsifiers.
- Suitable nonionic protective colloids are, for example, polyvinyl alcohols, polyvinyl acetals, polyvinylpyrrolidones, polysaccharides in water-soluble form, e.g.
- Suitable nonionic emulsifiers are, for example, surfactants such as alkylpolyglycol ethers or alkylarylpolyglycol ethers having from 8 to 40 alkylene oxide units.
- Cationically stabilized polymers dispersed in water it is possible, for example, to mix aqueous dispersions of base polymers with cationic protective colloids.
- Cationically stabilized polymers dispersed in water can also be obtained by redispersing cationically stabilized polymers which can be redispersed in water by means of water.
- the cationically stabilized polymer contains a total amount of from 0.1 to 20% by weight, preferably from 1 to 12% by weight, of the cationic protective colloid, if appropriate in combination with a nonionic protective colloid and/or nonionic emulsifier, in each case based on the polymeric constituents of the cationically stabilized polymers.
- Cationically stabilized polymers in the form of aqueous dispersions have a solids content of preferably from 10 to 75% by weight, particularly preferably from 40 to 60% by weight.
- the invention further provides a process for producing the aqueous preparations of the polymer-modified setting accelerators, characterized in that one or more setting accelerators and one or more cationically stabilized polymers are mixed in the presence of water.
- the setting accelerators can be used in any form for producing the aqueous preparations of the polymer-modified setting accelerators; i.e. the setting accelerators can, for example, be used in solid or liquid form or as aqueous solution, aqueous emulsion or aqueous dispersion.
- the cationically stabilized polymers are used as aqueous dispersions or as pulverulent polymers.
- Aqueous preparations of the polymer-modified setting accelerators can be produced, for example, by dispersing pulverulent cationically stabilized polymers in aqueous preparations of setting accelerators, for example dispersions or solutions. It is likewise possible to mix pulverulent cationically stabilized polymers with pulverulent setting accelerators to give dry mixes and to mix these with water at a later point in time to give the aqueous preparations of the polymer-modified setting accelerators.
- Aqueous preparations of the polymer-modified setting accelerators are preferably produced by mixing aqueous dispersions of cationically stabilized polymers with setting accelerators and if appropriate drying these to give powders which can be mixed again with water at a later point in time, for example on the construction site.
- the setting accelerators and the cationically stabilized polymers can be present in any ratios in the aqueous preparations of the polymer-modified setting accelerators.
- the weight ratio of cationically stabilized polymers to setting accelerators is preferably from 5:1 to 1:5, particularly preferably from 2:1 to 1:2 and most preferably 1:1, in each case based on the dry weight of the aqueous preparations of the polymer-modified setting accelerators.
- the aqueous preparations of polymer-modified setting accelerators are characterized in that they are stable and do not coagulate or precipitate in any mixing ratios even after days and weeks.
- the aqueous preparations of the polymer-modified setting accelerators are suitable for use in hydraulically setting systems, for example in concrete, mortars, for example in screeds or plasters and renders, and also paints.
- a preferred field of use for the aqueous preparations of the polymer-modified setting accelerators is use in concrete according to the dry spray concrete process and the wet spray concrete process.
- the invention further provides aqueous concrete compositions comprising cement, fillers and, if appropriate, further auxiliaries or additives, characterized in that an aqueous preparation of the polymer-modified setting accelerators is present.
- additives which modulate the setting-accelerating effect of the setting accelerators on the aqueous concrete compositions for example phosphoric acid, phosphonic acid, polyphosphate, polyhydroxycarboxylic acid or organic additives, in particular polyacrylic acid, hexamethylenetetramine, alkanolamines such as diethanolamine (DEA) or triethanolamine, can, if appropriate, be added to the aqueous concrete compositions.
- phosphoric acid for example phosphoric acid, phosphonic acid, polyphosphate, polyhydroxycarboxylic acid or organic additives, in particular polyacrylic acid, hexamethylenetetramine, alkanolamines such as diethanolamine (DEA) or triethanolamine
- DEA diethanolamine
- the invention further provides a process for producing the aqueous concrete composition by mixing of cement, fillers and, if appropriate, further auxiliaries or additives, characterized in that at least one aqueous preparation of the polymer-modified setting accelerators is added.
- the aqueous preparations of the polymer-modified setting accelerators are mixed with the further components of the aqueous concrete composition in the spray nozzle in the wet spray concrete process or the dry spray concrete process.
- Particular preference is given to use in the wet spray concrete process.
- the apparatuses known for spray concrete processes for example spraying robots or spraying machines, can be used.
- the aqueous preparations of the polymer-modified setting accelerators are advantageously delivered directly to the construction site, so that no time-consuming dispersing or dissolution and mixing of the setting accelerators and cationically stabilized polymers has to be carried out at the construction site.
- the mixing of the aqueous preparations of the polymer-modified setting accelerators with the further components of the aqueous concrete composition can be carried out by the wet spray concrete process or the dry spray concrete process using customary apparatuses and the established construction site logistics.
- a concrete mix having the same composition comprising cement, fillers and, if appropriate, further auxiliaries and additives can be used for the entire construction project and cationically stabilized polymers and setting accelerators can be added in the required amount to this concrete mix according to the requirements of each section of the construction during processing on the construction site.
- the aqueous concrete compositions of the invention also have advantageous use properties compared to conventional concrete compositions.
- the aqueous concrete compositions have, especially after a short setting time (1 to 2 days), increased compressive strength compared to conventional concrete compositions.
- the present invention further provides a process for producing a concrete composite, characterized in that one or more layers of the aqueous concrete compositions are applied on top of one another, with components being able, if appropriate, to be installed between or in the layers.
- Civil engineering encompasses any type of constructions such as buildings, shafts, supply routes, bridges, floor slabs or preferably tunnels or mines.
- the shuttering construction method the use of prefabricated concrete components or preferably the spray concrete process are employed.
- Prefabricated components can be obtained by introducing aqueous concrete compositions into molds which are removed after setting of the aqueous concrete compositions.
- the aqueous concrete compositions are preferably applied directly to the substrate which may, if appropriate, be reinforced with steel.
- the applied layer thickness is usually in the range from 10 to 40 cm.
- water-impermeable films or water-impermeable membranes are installed between a component and a layer of an aqueous concrete composition or between two layers of aqueous concrete compositions, each of which may, independently of one another, be reinforced with steel.
- aqueous dispersion of the cationic polymer use was made of a vinyl acetate-ethylene copolymer dispersion which had a solids content of 50% by weight and a Tg of ⁇ 5° C. and had been produced in the presence of 10% by weight of polytrimethylammoniopropylmethacrylamide chloride, based on the mass of the vinyl acetate and ethylene monomers used.
- aqueous preparations of the polymer-modified setting accelerators were produced by introducing an aqueous dispersion of aluminum sulfate into the cationic polymer dispersed in water in the amounts indicated below while stirring with an Ultraturrax stirrer and under standard conditions in accordance with DIN50014 and stirring the mixture for 5 minutes.
- the wet concrete mix was made up with 146 kg of water.
- the wet concrete mix was made up with 156 kg of water. No cationically stabilized polymer dispersed in water was used.
- aqueous preparations of the polymer-modified setting accelerators bring about an increase in the compressive strengths of set, aqueous concrete compositions (example 2) compared to conventional set concrete compositions (comparative examples 2 and 3).
- the set, aqueous concrete compositions according to aspects of the invention have an increased early strength.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inorganic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Paints Or Removers (AREA)
- Civil Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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DE102007024965A DE102007024965A1 (de) | 2007-05-30 | 2007-05-30 | Wässrige Zubereitungen polymermodifizierter Abbindebeschleuniger und deren Einsatz im Baubereich |
DE102007024965.0 | 2007-05-30 | ||
DE102007024965 | 2007-05-30 | ||
PCT/EP2008/055958 WO2008145531A2 (fr) | 2007-05-30 | 2008-05-15 | Préparations aqueuses d'accélérateurs de prise modifiés par des polymères et leur utilisation dans le domaine de la construction |
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US20100303549A1 US20100303549A1 (en) | 2010-12-02 |
US9242904B2 true US9242904B2 (en) | 2016-01-26 |
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US12/599,982 Expired - Fee Related US9242904B2 (en) | 2007-05-30 | 2008-05-15 | Aqueous preparations of polymer-modified setting accelerators, and use thereof in the construction industry |
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US (1) | US9242904B2 (fr) |
EP (1) | EP2152647B2 (fr) |
CN (1) | CN101679132B (fr) |
AT (1) | ATE556993T1 (fr) |
AU (1) | AU2008257740B2 (fr) |
DE (1) | DE102007024965A1 (fr) |
RU (1) | RU2456252C2 (fr) |
WO (1) | WO2008145531A2 (fr) |
ZA (1) | ZA200906420B (fr) |
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US11634556B2 (en) | 2020-11-27 | 2023-04-25 | Jiangsu Arit New Materials Co., Ltd. | Method for preparing accelerator for sprayed mortar/concrete |
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DE102008043516A1 (de) | 2008-11-06 | 2010-05-12 | Wacker Chemie Ag | Verfahren zur Applikation von polymermodifizierten Nassbetonmischungen |
EP2248780A1 (fr) * | 2009-05-06 | 2010-11-10 | BK Giulini GmbH | Accélérateur de prise et de durcissement |
CN107963846B (zh) * | 2017-12-29 | 2020-06-09 | 成都精准混凝土有限公司 | 一种喷射混凝土及其制备方法 |
BE1030214B1 (de) * | 2023-02-02 | 2023-08-18 | Gansu Construction Invest Foundation Engineering Co Ltd | Bauverfahren für eine lang aufgebohrte, hochfeste, einfach bewehrte, auftriebssichernde Ankerstange in Sandsteinformationen |
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DE2011150A1 (en) | 1970-03-10 | 1971-09-30 | Ludwig Horlmg Fabrik chemischer Baustoffe GmbH, 3283 Lugde | Organic additives for the rapid setting of concrete |
US3931096A (en) | 1974-10-30 | 1976-01-06 | Calgon Corporation | Low fluid loss cementing compositions |
DE2548688A1 (de) | 1975-10-30 | 1977-05-05 | Ullrich Fritz | Zusatzmittel fuer moertel und beton zum beschleunigen des erstarrungsbeginnes |
JPS57166351A (en) | 1981-03-31 | 1982-10-13 | Kuraray Co | Cement composition |
US5229019A (en) * | 1986-02-24 | 1993-07-20 | Forrest Gabriel T | Low fluid leakoff cementing compositions and filtration control additive for cement |
EP0812812A1 (fr) | 1996-06-14 | 1997-12-17 | Mbt Holding Ag | Additif pour béton projeté |
WO2000005275A1 (fr) | 1998-07-22 | 2000-02-03 | Elotex Ag | Poudre redispersible, sa dispersion aqueuse, son procede de preparation et ses utilisations |
WO2000005276A1 (fr) | 1998-07-22 | 2000-02-03 | Elotex Ag | Procede de preparation de dispersions aqueuses de particules de latex de morphologie heterogene, particules de latex ainsi obtenues, dispersions et poudres redispersibles associees, et leurs utilisations |
US6395853B1 (en) * | 1999-06-10 | 2002-05-28 | Clariant Gmbh | Water-soluble copolymers and their use for exploration and production of petroleum and natural gas |
US20050194323A1 (en) * | 2004-03-04 | 2005-09-08 | U.S. Filter/Scaltech, Inc. | System and method for recovering oil from a waste stream |
JP2006045010A (ja) | 2004-08-05 | 2006-02-16 | Kao Corp | 水硬性組成物用添加剤 |
US20070037925A1 (en) * | 2003-04-17 | 2007-02-15 | Wacker Polymer System Gmbh & Co. Kg | Redispersion powder composition with a binding acceleration effect |
DE102006007282A1 (de) | 2006-02-16 | 2007-08-23 | Wacker Polymer Systems Gmbh & Co. Kg | Verfahren zur Herstellung von kationisch stabilisierten und in Wasser redispergierbaren Polymerpulverzusammensetzungen |
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RU2143341C1 (ru) * | 1993-07-21 | 1999-12-27 | Э.Хашогги Индастриз | Изделие, изготовленное из неорганически наполненного материала, способ его изготовления и устройство для его осуществления (варианты) |
DE4402408A1 (de) * | 1994-01-27 | 1995-08-03 | Wacker Chemie Gmbh | Redispergierbare, siliciummodifizierte Dispersionspulverzusammensetzung, Verfahren zu deren Herstellung und deren Verwendung |
NO302538B1 (no) * | 1995-05-30 | 1998-03-16 | Reslab As | Framgangsmåte for stabilisering av ukonsolidert kjernemateriale fra borehull |
AU723970B2 (en) * | 1996-06-14 | 2000-09-07 | Construction Research & Technology Gmbh | Concrete spraying additives |
DE19833066A1 (de) * | 1998-07-22 | 2000-02-03 | Elotex Ag Sempach Station | Verfahren zur Herstellung wäßriger Dispersionen von (Co-)Polymerisaten, die danach erhältlichen Dispersionen, aus den Dispersionen erhältliche redispergierbare Pulver sowie deren Verwendung |
DE10253045A1 (de) * | 2002-11-14 | 2004-06-03 | Wacker Polymer Systems Gmbh & Co. Kg | In Wasser redispergierbare Polymerpulver-Zusammensetzungen mit abbindebeschleunigender Wirkung |
-
2007
- 2007-05-30 DE DE102007024965A patent/DE102007024965A1/de not_active Ceased
-
2008
- 2008-05-15 RU RU2009148602/03A patent/RU2456252C2/ru not_active IP Right Cessation
- 2008-05-15 AU AU2008257740A patent/AU2008257740B2/en not_active Ceased
- 2008-05-15 US US12/599,982 patent/US9242904B2/en not_active Expired - Fee Related
- 2008-05-15 WO PCT/EP2008/055958 patent/WO2008145531A2/fr active Application Filing
- 2008-05-15 CN CN2008800178543A patent/CN101679132B/zh not_active Expired - Fee Related
- 2008-05-15 EP EP08750301.7A patent/EP2152647B2/fr not_active Not-in-force
- 2008-05-15 AT AT08750301T patent/ATE556993T1/de active
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2009
- 2009-09-15 ZA ZA200906420A patent/ZA200906420B/xx unknown
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DE2011150A1 (en) | 1970-03-10 | 1971-09-30 | Ludwig Horlmg Fabrik chemischer Baustoffe GmbH, 3283 Lugde | Organic additives for the rapid setting of concrete |
US3931096A (en) | 1974-10-30 | 1976-01-06 | Calgon Corporation | Low fluid loss cementing compositions |
DE2548688A1 (de) | 1975-10-30 | 1977-05-05 | Ullrich Fritz | Zusatzmittel fuer moertel und beton zum beschleunigen des erstarrungsbeginnes |
JPS57166351A (en) | 1981-03-31 | 1982-10-13 | Kuraray Co | Cement composition |
US5229019A (en) * | 1986-02-24 | 1993-07-20 | Forrest Gabriel T | Low fluid leakoff cementing compositions and filtration control additive for cement |
EP0812812A1 (fr) | 1996-06-14 | 1997-12-17 | Mbt Holding Ag | Additif pour béton projeté |
WO2000005275A1 (fr) | 1998-07-22 | 2000-02-03 | Elotex Ag | Poudre redispersible, sa dispersion aqueuse, son procede de preparation et ses utilisations |
WO2000005276A1 (fr) | 1998-07-22 | 2000-02-03 | Elotex Ag | Procede de preparation de dispersions aqueuses de particules de latex de morphologie heterogene, particules de latex ainsi obtenues, dispersions et poudres redispersibles associees, et leurs utilisations |
US6395853B1 (en) * | 1999-06-10 | 2002-05-28 | Clariant Gmbh | Water-soluble copolymers and their use for exploration and production of petroleum and natural gas |
US20070037925A1 (en) * | 2003-04-17 | 2007-02-15 | Wacker Polymer System Gmbh & Co. Kg | Redispersion powder composition with a binding acceleration effect |
US20050194323A1 (en) * | 2004-03-04 | 2005-09-08 | U.S. Filter/Scaltech, Inc. | System and method for recovering oil from a waste stream |
JP2006045010A (ja) | 2004-08-05 | 2006-02-16 | Kao Corp | 水硬性組成物用添加剤 |
DE102006007282A1 (de) | 2006-02-16 | 2007-08-23 | Wacker Polymer Systems Gmbh & Co. Kg | Verfahren zur Herstellung von kationisch stabilisierten und in Wasser redispergierbaren Polymerpulverzusammensetzungen |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11634556B2 (en) | 2020-11-27 | 2023-04-25 | Jiangsu Arit New Materials Co., Ltd. | Method for preparing accelerator for sprayed mortar/concrete |
Also Published As
Publication number | Publication date |
---|---|
WO2008145531A3 (fr) | 2009-02-12 |
CN101679132A (zh) | 2010-03-24 |
ZA200906420B (en) | 2010-05-26 |
WO2008145531A2 (fr) | 2008-12-04 |
AU2008257740A1 (en) | 2008-12-04 |
EP2152647B2 (fr) | 2015-12-02 |
RU2456252C2 (ru) | 2012-07-20 |
RU2009148602A (ru) | 2011-07-10 |
ATE556993T1 (de) | 2012-05-15 |
US20100303549A1 (en) | 2010-12-02 |
AU2008257740B2 (en) | 2010-12-09 |
CN101679132B (zh) | 2012-12-19 |
EP2152647B1 (fr) | 2012-05-09 |
EP2152647A2 (fr) | 2010-02-17 |
DE102007024965A1 (de) | 2008-12-04 |
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